EP3316687A1

EP3316687A1 - Thermodynamically stable crystal modification of 2-chloro-3-(methylsulfanyl)-n-(1-methyl-1h-tetrazol-5-yl)-4-(trifluoromethyl)benzamide

Info

Publication number: EP3316687A1
Application number: EP16734325.0A
Authority: EP
Inventors: Hartmut Ahrens; Arnim Köhn; Christian Waldraff; Britta Olenik; Birgit Keil
Original assignee: Bayer CropScience AG
Current assignee: BASF SE
Priority date: 2015-07-03
Filing date: 2016-06-30
Publication date: 2018-05-09
Also published as: MX2018000308A; KR20180022976A; EA201890207A1; JP2018522870A; AU2016289664A1; CN107846885A; CA2990983A1; US20180208563A1; WO2017005585A1; ZA201708745B; BR112018000094A2

Abstract

The invention relates to a thermodynamically stable crystal modification of 2-chloro-3-(methylsulfanyl)-n-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide. This thermodynamically stable crystal modification has particular advantages regarding the stability of suspension formulations.

Description

description

Thernnodynannically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide

The invention relates to the technical field of pesticides.

More particularly, it relates to a thermodynamically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide of the formula (I)

And a process for their preparation and their use as a herbicide. The compound of the formula (I) will hereinafter be understood independently of its

Appearance known as "benzamide".

It is known that some organic compounds in only one crystal structure, while others, so-called polymorphs, can occur in different crystal structures, see, for example, J. Bernstein, R.J. Davey, J.O. Henck, Angew. Chem. Int. Ed., 1999, 38, 3440-3461. Thus, EP 1 314 724 A1 discloses two crystal structures of the herbicidal active substance sulcotrione.

The benzamide known, for example, from WO 2012/028579 A1 (there Example No. 4-638 in Table 4) has herbicidal properties and is suitable for the

Production of pesticides used for weed control. However, it has been found that this according to the disclosure of

Benzamide which can be prepared is not suitable for the production of user-friendly administration forms. user-friendly Dosage forms are, for example, suspension formulations in which the benzamide is finely ground in solid form. Practical testing has shown that the benzamide prepared in accordance with the disclosure of WO 2012/028579 A1 in suspension formulations leads to crystal growth and as a result to lumps and precipitations, so that the suspension formulation becomes unusable. The crystal growth can occur spontaneously or over a longer period of time and can not be predicted.

The object of the present invention was to provide a modification of the benzamide which overcomes these disadvantages and is suitable for the preparation of a storage-stable suspension formulation over a relatively long period of time.

In the context of the present invention, it has been found that the benzamide occurs in a thermodynamically metastable and in a thermodynamically stable crystal modification.

In the context of the present invention it has also been found that the

thermodynamically stable crystal modification of the benzamide does not have the abovementioned disadvantages and is therefore particularly suitable for the preparation of suspension formulations such as suspooconcentrates, suspoemulsions and oil dispersions.

In addition, the benzamide preparable according to the disclosure of WO 2012/028579 A1 has the disadvantage that it works less well, can be filtered and cleaned. This disadvantage is overcome by the provision of the thermodynamically stable benzamide according to the invention.

An object of the invention is therefore a thermodynamically stable

Crystal modification of the benzamide 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide).

The following is the metastable crystal modification of the benzamide as "metastable crystal modification I" and the stable called "stable crystal modification II". The terms "modification" and "crystal modification" are used in the

Below understood as synonymous.

The metastable crystal modification I has a characteristic Raman spectrum, which is shown in Figure 1, with the values of the band maxima in wavenumbers given in Table 1.

The X-ray powder diffractometry of the metastable crystal modification I shows characteristic peaks which are given in Table 2 for this crystal modification. The accompanying X-ray diffractogram is shown in Figure 3.

The stable crystal modification II also exhibits a characteristic Raman spectrum, which is shown in FIG. 2, wherein the values of the band maxima in wavenumbers are also given in Table 1.

The X-ray powder diffractometry of the stable crystal modification II shows characteristic peaks for this crystal modification, which are also given in Table 2. The accompanying X-ray diffractogram is shown in Figure 4.

Table 1: Band maxima of the Raman spectra [cm ^-1 ] metastable modification I stable modification II

3091 3086

3071 3058

3020 3034

3002 3008

2964 2968

2942 2935

2933 1690

2857 1590

2835 1549

1710 1464

1699 1452 metastable modification 1 stable modification II

1591 1425

1553 1404

1459 1363

1424 1313

1366 1283

1303 1257

1287 1245

1251 1181

1185 1151

1143 1112

1117 1101

1102 1074

1073 1044

1047 936

984 836

975 792

929 769

857 743

790 702

759 680

737 641

719 607

704 491

696 474

687,426

635,376

608,353

572 321

488 301

467 269

446 234

408 221

381 199

346 175

325 109 metastable modification 1 stable modification II

306

274

240

182

167

141

109

measurement conditions

Device Bruker Raman RFS 100 / S

Number of scans 64

Resolution 2 cm ^"1

Laser power 50 mW

Laser wavelength 1064 nm

Table 2: X-ray powder diffractometry pattern

Peak maximum [2 theta]

metastable modification I stable modification II

8.1 6.7

9.7 1 1, 3

1 1 .2 13.6

12.5 14.0

13.3 15.1

13.5 17.1

15.6 18.0

15.7 20.0

16.1 20.3

16.7 20.5

17.1 20,7

17.7 21, 5

18.2 22.2 Peak maxima [2 theta] metastable modification 1 stable modification II

18.7 22.6

19.2 22.8

19.4 23.5

20.0 23.9

20.5 24.1

20.8 24.8

21 .0 26,0

21 .2 26,9

21 .9 27.4

22.3 28.2

22.6 28.5

23.0 29.7

23.4 30.0

24.1 30.7

24.4 31, 5

24.7 31, 6

25.1 32.2

25.1 32,8

25.6 33.3

26.0 33.6

26.2 34.6

26.5 35.4

26.8 35,8

27.2 36.4

27.4 36.9

27.7

28.3

28.7

28.8

29.3

29.5 Peak maxima [2 theta] metastable modification 1 stable modification II

30.2

30.5

30.6

30.9

31 .6

31 .7

32.3

32.6

32.7

33.0

33.1

33.3

33.7

33.9

34.0

34.3

34.6

34.7

34.9

35.9

36.4

36.9

37.0

37.3

37.4

37.9

Measurement conditions:

Scan Axis Gonio

Start Position [° 2Th.] 2.0066

End position [° 2Th.] 37.9906

Anode, material Cu

K-alpha1 [A] 1 .54060 K-alpha2 [A] 1 .54443

K-Beta [A] 1 .39225

K-A2 / K-A1 Ratio 0.50000

Generator Settings 40 mA, 40 kV

Incident beam monochromator focusing x-xay mirror

Spinning Yes

To determine the Raman spectra, at least two spectra, each containing 128 scans, of each lot were recorded by means of an RFS 100 / S FT-Raman from Bruker.

Single-crystal X-ray diffraction analysis was determined by using a M18X-HF rotating anode with ΜοΚα radiation from MACScience Co and a SMART CCD-1000 detector from Bruker-AXS. The data were processed with the programs SAINT-NT V 5.0 (data reduction, Bruker-AXS) and SADABS (absorption correction, Bruker-AXS). The structure solution and refinement was performed with SHELXTL NT version V5.1.

The benzamide of the formula (I) per se can be prepared, for example, by one of the methods mentioned in WO 2012/028579 A1. Depending on the nature of the solvent used in the last purification step and the temperature control, the benzamide usually accumulates in amorphous form, in the form of the metastable crystal modification I described here or in a mixture of the amorphous form and the metastable crystal modification I.

The thermodynamically stable crystal modification II of the benzamide can

for example, be prepared in a general manner by suspending and / or dissolving the benzamide obtainable according to WO 2012/028579 A1 in a suitable solvent and converting it to quantitative conversion

thermodynamically stable crystal modification II treated at temperatures of 0 ° C to 80 ° C.

Another object of the invention is thus a process for the preparation of the thermodynamically stable crystal modification II of the benzamide, wherein the Crystal modification I of the benzamide is suspended in solvents and / or dissolved and treated until the quantitative conversion into the thermodynamically stable crystal modification II at temperatures of 0 ° C to 80 ° C.

Suitable solvents which can be used in this process are e.g. lower alcohols such as methanol, ethanol, 2-propanol or ketones such as acetone, 2-butanone, which can also be used in admixture with water. As lower alcohols or ketones are here referred to those compounds having one to ten carbon atoms, preferably one to five carbon atoms.

Other suitable solvents are benzene, toluene and chlorobenzene. Preference is given to toluene and mixtures of ethanol and water, more preferably toluene and a mixture of ethanol and water in a ratio of 1: 1.

The conversion into the thermodynamically stable crystal modification II is carried out at temperatures below 100 ° C, preferably at temperatures of 0 ° C to 80 ° C, more preferably at temperatures of 20 ° C to 80 ° C, most preferably at temperatures of 20 ° C. up to 40 ° C. The duration of the conversion depends on the temperature and the type of solvent. Furthermore, the duration of the conversion depends on whether seed crystals of crystal modification II are used. In general, the conversion to the crystal modification II at full dissolution of the crystals of the crystal modifications I at elevated

Temperature can be achieved directly by cooling crystallization to room temperature without the use of seed crystals. The cooling to room temperature is preferably carried out with a cooling rate of less than 25 ° C, more preferably with a cooling rate of less than 20 ° C. The conversion of a suspension of

Crystal modifications I can usually be accomplished without the use of seed crystals over a 14 day period. If seed crystals of the crystal modification II are used in the conversion of a suspension, is

Generally a treatment time of 24 to 48 hours sufficient to achieve a quantitative conversion of the crystals in the crystal modification II.

The obtained crystal of the crystal modification II are finally separated and dried to constant weight for removal of the solvent at room temperature or elevated temperature.

The stable crystal modification II can also be obtained by grinding under high pressure from the crystal modification I or the amorphous form. Suitable pressure is a pressure of at least 5 bar.

Due to its stability, the crystal modification II is outstandingly suitable for the preparation of formulations, in particular suspension formulations of crop protection agents. The invention therefore also

Plant protection products containing the crystal modification II of benzamide alone or in admixture with excipients and carriers, as well as in admixture with other active ingredients. The invention also includes mixtures of the crystal modification II of the benzamide with the crystal modification I of the benzamide, e.g. those which at any point in the inventive conversion process of the

Crystal modifications I occur in the crystal modification II. Preference is given to an active ingredient quality with more than 80% by weight of the crystal modification II of the benzamide, particularly preferably more than 90% by weight, very particularly preferably more than 95% by weight and most preferably more than 98% by weight .-%.

Optionally, the benzamide of the stable crystal modification II is mixed with one or more other herbicides. Such mixtures also benefit from the advantageous properties of the inventive crystal modification II.

Due to their stability, the stable crystal modification II of benzamide is generally suitable as starting material for the preparation of any of these benzamide-containing crop protection formulations, even if the benzamide is no longer in this form after formulation, but rather in dissolved form.

The invention therefore also relates to processes for the preparation of

Benzamide-containing crop protection formulations containing the stable

Use crystal modification II of the benzamide and this benzamide containing Pflanzenschutzfornnulierungen obtained from the stable crystal modification II of the benzamide. Through the use of stable

Crystal modification II increases the safety of preparations of benzamide and thus reduces the risk of incorrect dosages.

The stable crystal modification II of the benzamide can be converted in a known manner into the customary formulations, such as suspension concentrates, colloidal concentrates, dispersible concentrates, emulsifiable concentrates

(Emulsion concentrates), emulsion mordants, suspension mordants, granules,

Microgranules, suspoemulsions, oil dispersions, water-soluble granules, water-soluble concentrates and water-dispersible granules, using suitable auxiliaries and carriers or solvents. Here is the effective

Compound in a concentration of about 0.5 to 90 wt .-% of

Overall mixture may be present, i. in amounts sufficient to achieve the necessary dosage level. The formulations are prepared, for example, by hiding the stable crystal modification II of the benzamide with solvents and / or carriers, optionally under

Use of emulsifying and / or dispersing agents, and / or others

Auxiliaries, such as Penetration aids.

The application is carried out in the usual way by contacting the undesired plants and / or their habitat with the active ingredient or its formulation.

In addition, the thermodynamically stable crystal modification II of the benzamide can be worked up, filtered and purified particularly well.

The benzamide in the stable crystal modification II shows excellent herbicidal activity against representatives of the group of both monocotyledonous and dicotyledonous plants. Examples include:

Dicotyledonous plants of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenociea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

Monocotyledonous plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata , Ishumum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

The invention is therefore also the use of stable

Crystal modification II of the benzamide for the preparation of a crop protection agent for the treatment of weed infestation.

The stable crystal modification II of the benzamide according to the invention is due to its high compatibility with crops to combat

undesirable plants in crops of, for example, wheat, barley, oats, rye, rice, maize, sugar beet, sugarcane, cotton and soy, especially in wheat, barley, oats and rye.

According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants produced by conventional breeding and optimization methods or by

biotechnological and genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and including plant varieties that can be protected or not protected by plant variety rights. Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative

Propagating material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and plant parts with the inventive crystal modification II of the benzamide is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, evaporating, misting, spreading or brushing on.

The inventive crystal modification II of the benzamide can, as already stated above, be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active substance-impregnated nature - and synthetic substances and Feinstverkapselungen in polymeric materials.

These formulations are prepared in a known manner, for. B. by

Mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or

foaming agents.

In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are: e.g. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite,

Montmorillonite or diatomaceous earth and ground synthetic minerals, such as

highly dispersed silicic acid, alumina and silicates, as solid carriers for granules are suitable: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin sulphite liquors and methylcellulose.

It can be used in the formulations adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural

Phospholipids such as cephalins and lecithins and synthetic phospholipids.

Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and

Metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of the active ingredient in the inventive crystal modification II, preferably between 0.5 and 90%.

The invention Kristallmod ifikation II of benzamide can be used as such or in their formulations in admixture with known herbicides and / or with substances that improve the crop plant compatibility ("safeners") for weed control, ready-made formulations or

Tank mixes are possible. So there are also mixtures with

Weedkillers containing one or more known herbicides and a safener are possible.

For the mixtures are known herbicides in question, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium),

Ametryne, Amicarbazone, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidine, Azimsulfuron, Beflubutamide, Benazoline (-ethyl), Benfuresate, Bensulfuron (-methyl), Bentazone, Benzfendizone, Benzobicyclone, Benzofenap, Benzoylprop (- ethyl), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxime, Bromoxynil, Butachlor, Butafenacil (-allyl), Butroxydim, Butylates, Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, chlorsulfuron, chlortoluron, cinidone (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, Cycloate, Cydosulfamuron, Cydoxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, Desmedipham, Diallate, Dicamba, Dichlorprop (- P), Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepip erate, dimethachlor, dimethametryn,

Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, Epropodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanide, Fenoxaprop (-P-ethyl), Fentrazamide, Flamprop ( -isopropyl, -isopropyl-L, -methyl), flazasulfuron,

Florasulam, Fluazifop (-P-butyl), Fluazolate, Flucarbazone (-sodium), Flufenacet, Flumetsulam, Flumiclorac (-pentyl), Flumioxazin, Flumipropyn, Flumetsulam,

Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurpyrsulfuron (-methyl, -sodium), Flurenol (-butyl), Fluridone, Fluroxypyr (-butoxy-propyl, -meptyl), Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide,

Fomesafen, foramsulfuron, glufosinate (-ammonium), glyphosate (- isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, -P-methyl), hexazinone, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron , iodosulfuron (-methyl, -sodium), loxynil, isopropalin, isoproturon, isourone, isoxaben, isoxachlorotole, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfuron (-methyl, -sodium), mesotrione, metamitron , Metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha) metolachlor, metosulam, metoxuron, metribuzin,

Metsulfuron (-methyl), molinates, monolinuron, naproanilides, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon,

Oxasulfuron, oxaziclomefones, oxyfluorfen, paraquat, pelargonic acid,

Pendimethalin, Pendralin, Pentoxazone, Phenmedipham, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulfuron (-methyl), Profluazole, Prometry, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone (-sodium), Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl ), Pyrasulfotols, pyrazogyl, pyrazolates, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridates, pyridatol, pyriftalid, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamines, quizalofop (-P-ethyl , -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchloro, thiafluamides, thiazopyr, thidiazimin, thifensulfuron (-methyl) , Thiobencarb, tiocarbazil,

Tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron.

Other suitable safeners for the mixtures are, for example, AD-67, BAS-145138, benoxacor, cloquintocet (-mexyl), cyometrinil,

Cyprosulfamides, 2,4-D, DKA-24, Dichlormid, Dymron, Fenclorim, Fenchlorazole (- ethyl), Flurazoles, Fluxofenim, Furilazoles, Isoxadifen (-ethyl), MCPA, Mecoprop (-P), Mefenpyr (-diethyl), MG-191, oxabetrinil, PPG-1292, R-29148. Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, bird repellents,

Plant nutrients and soil conditioners are possible.

The inventive crystal modification II of the benzamide can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, sprinkling.

The inventive crystal modification II of the benzamide can be applied both before and after emergence of the plants. It can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 1 g and 1 kg of active ingredient per hectare of soil surface, preferably between 5 g and 500 g per ha.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild

occurring or treated by conventional biological breeding methods, such as crossing or protoplast fusion, plant species and plant varieties and their parts. In a further preferred embodiment, transgenic plants and plant cultivars are obtained by genetic engineering methods

optionally in combination with conventional methods were obtained (Genetically Modified Organrns) and treated their parts. The term "parts" or "parts of plants" or "plant parts" has been explained above. It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are understood to be plants having certain traits which have been obtained both by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, biotypes and genotypes.

Depending on plant species or plant varieties, their location and

Growth conditions (soils, climate, vegetation period, diet) can also be superadditive ("synergistic") effects occur by the treatment according to the invention. Thus, for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents that can be used according to the invention - also in combination with other agrochemical active ingredients -, better plant growth of crops, increased tolerance of crops against high or low temperatures, increased Tolerance of crops against drought or against water or soil salt content, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the crop

Harvest products, higher shelf life and / or workability of the harvested products possible, which go beyond the expected effects actually.

Among the preferred according to the invention to be treated transgenic

(Genetically engineered) plants or plant varieties include all plants that received genetic material by the genetic modification, which gives these plants special beneficial properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products. More and more

highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active ingredients. As examples

Transgenic plants are the major crops, such as cereals (wheat, rice), soybean, potato, cotton, oilseed rape and especially corn and fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentioned, whereby in particular corn, in addition, soy, potato, cotton and oilseed rape

be highlighted. Traits which are particularly emphasized are the increased defense of the plants against insects by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (a), CrylA (b), CrylA (c), CryllA, CrylllA, CrylllB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and their

Combinations) are produced in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones.

Sulfonylureas, glyphosate or phosphinotricin (e.g., "PAT" gene). The genes which confer the desired properties ("traits") can also be identified in

Combinations occur together in the transgenic plants. As examples of "Bt plants" are v.a. Maize varieties, but also cottons, soya and potato varieties sold under the trade names YIELD GARD® (e.g., corn, cotton, soy), KnockOut® (e.g., corn), StarLink® (e.g., corn),

Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). As examples of herbicide tolerant plants are v.a. Maize varieties, but also called cotton varieties and soybean, among the

Trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance to imidazolinone) and STS® (tolerance to sulfonylureas eg corn). Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits. embodiments

Preparation of the thermodynamically stable crystal modification II

Variant 1: 0.1 g of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1 were suspended in 0.5 ml of ethanol: water (1: 1). The suspension is shaken at 25 ° C and stirred for 24 hours at 20 to 25 ° C. Then another 0.5 ml of ethanol: water (1: 1) are added and stirred at 20 to 25 ° C for 8 days. The suspension is filtered and the residue is left open at room temperature until the solvent has evaporated. You get that

Benzamide in the thermodynamically stable crystal modification II.

Variant 2: 0.1 g of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1 were suspended in 0.25 ml of toluene. The suspension is shaken at 25 ° C and stirred for 24 hours at 20 to 25 ° C. Then another 0.25 ml of toluene are added and stirred at 20 to 25 ° C for 6 days. Again, another 0.25 ml of toluene are added and stirred at 20 to 25 ° C for 2 days. The

Suspension is left open at room temperature until the solvent has evaporated. The benzamide is obtained in the thermodynamically stable

Crystal modification II.

stability tests

An oil dispersion of the benzamide of the crystal modification II shows in comparison to an oil dispersion of the benzamide prepared according to the methods disclosed in WO 2012/028579 A1, even after several weeks of storage, no signs of lumping and precipitation.

Claims

claims

1 . Thernnodynannically stable crystal imodification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (thfluoromethyl) -benzannide, in which the

Kristal I mod if i cation

a) has a Raman spectrum with band maxima [cm ^-1 ] of:

3086 1044

3058 936

3034 836

3008 792

2968 769

2935 743

1690 702

1590 680

1549 641

1464 607

1452 491

1425 474

1404 426

1363 376

1313 353

1283 321

1257 301

1245 269

1 181 234

1 151 221

1 1 12 199

1 101 175

1074 109 and

b) an X-ray powder diffractometry pattern with the following peaks, expressed in degrees 2 theta, comprising:

2. Herbicidal agent, characterized by a content of the

Thermodynamically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide according to claim 1 and common extenders and / or surface-active adjuvants.

3. A herbicidal composition containing the thermodynamically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) A benzamide according to claim 1 or 2 and a metastable crystal modification, characterized in that the 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide more than 90 wt .-% is present in the stable crystal modification.

4. A herbicidal composition according to claim 3, characterized in that the 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1 H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide to more than 95 Wt .-% in the stable crystal modification is present.

5. A herbicidal composition according to claim 3, characterized in that the 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1 H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide to more than 98 Wt .-% in the stable crystal modification is present.

6. Use of the thermodynamically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide according to claim 1 or an agent according to one of Claims 2 to 5 for controlling undesirable plants.

7. A method of controlling unwanted plants, thereby

characterized in that the thermodynamically stable crystal modification of 2-chloro-3- (methylsulfanyl) -N- (1-methyl-1H-tetrazol-5-yl) -4- (trifluoromethyl) benzamide according to claim 1 or an agent according to a of claims 2 to 5 can act on the unwanted plants and / or their habitat.

8. The method of claim 7 for controlling harmful plants in

monocot plant crops.

9. The method of claim 7 or 8, wherein the crops are genetically engineered or obtained by mutation selection.